Organoleptic compounds

ABSTRACT

The present invention relates to novel compounds and their use as fragrance materials.

STATUS OF RELATED APPLICATIONS

This application is a continuation of U.S. provisional application61/869,060 filed Aug. 22, 2013, the content hereby incorporated byreference as if set forth in its entirety.

FIELD OF THE INVENTION

The present invention relates to new chemical entities and theincorporation and use of the new chemical entities as fragrancematerials.

BACKGROUND OF THE INVENTION

There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and other persons the ability to create newfragrances for perfumes, colognes and personal care products. Those withskill in the art appreciate how differences in the chemical structure ofthe molecule can result in significant differences in the odor, notesand characteristics of a molecule. These variations and the ongoing needto discover and use the new chemicals in the development of newfragrances allow the perfumers to apply the new compounds in creatingnew fragrances.

SUMMARY OF THE INVENTION

The present invention provides novel compounds and their unexpectedadvantageous use in enhancing, improving or modifying the fragrance ofperfumes, colognes, toilet water, fabric care products, personalproducts and the like.

More specifically, an embodiment of the present invention relates tonovel isobenzofuran compounds represented by Formula I,1,1-diethyl-4,6-dimethyl-1,3,3a,4 (or 6),7,7a-hexahydro-isobenzofuran,including Formula Ia and Ib and Formula II,1,1-diethyl-5,7-dimethyl-1,3,3a,4,5 (or 7),7a-hexahydro-isobenzofuran,including Formula IIa and IIb, which exhibit unexpected woody and spicynotes with leather-like quality, and a method of improving, enhancing ormodifying a fragrance formulation through the addition of an olfactoryacceptable amount of these isobenzofurans.

Another embodiment of the present invention relates to the advantageousfragrance use of a mixture of Formula III, cyclopentadecanone, andFormula IV, cyclopentadec-3-enone, which exhibits strong and creamymusk, musk ketone, caring and woody notes with an interesting floralcycharacter. Their structures are set forth below:

Another embodiment of the present invention relates to novel aldehydesrepresented by Formula V, 5-methyl-hept-5-enal, and Formula VI,2,4-dimethyl-hex-4-enal, which exhibit unexpected strong and complexfragrance effect of a melon-like ozonic note with a green aspect thatprovides a natural melon feel and a vegetable character, and a method ofimproving, enhancing or modifying a fragrance formulation through theaddition of an olfactory acceptable amount of theses aldehydes.

Another embodiment of the present invention relates to a novel aldehyde2,4,8-trimethyl-deca-4,9-dienal represented by Formula VII, whichexhibits unexpected powerful aldehydic green, floral and muguet noteswith high impact and very toppy characters, and a method of improving,enhancing or modifying a fragrance formulation through the addition ofan olfactory acceptable amount of this aldehyde.

Another embodiment of the present invention relates to novelbenzofuranones represented by Formula VIII,5-ethyl-3-methylhexahydro-1-benzofuran-2(3H)-one, and Formula IX,6-ethyl-3-methylhexahydro-1-benzofuran-2(3H)-one, which exhibitunexpected creamy, coconut-like and pleasant notes supported by anoverall woodiness and a slightly animalic character, reminiscent ofheliotropin and coumarin, and a method of improving, enhancing ormodifying a fragrance formulation through the addition of an olfactoryacceptable amount of theses benzofuranones.

Another embodiment of the present invention relates to a novel compoundmethyl-2-(propan-2-yl)cyclohexyl carbonate represented by Formula X,which exhibits unexpected apple and berry notes with a soft fruitycharacter further supported by a herbaceous, spicy, fresh and woodyquality, and a method of improving, enhancing or modifying a fragranceformulation through the addition of an olfactory acceptable amount ofthis compound.

Another embodiment of the present invention relates to a novel compound2-[3-methoxy-2-propen-1-yl]-6,6-dimethyl-bicyclo[3.1.1]hept-2-enerepresented by Formula XI, which exhibits unexpected white floral andmuguet characters topped by fresh, green and melon-like notes furthersupported by creamy and herbaceous quality, and a method of improving,enhancing or modifying a fragrance formulation through the addition ofan olfactory acceptable amount of this compound.

Another embodiment of the present invention relates to a novel compoundbut-2-enoic acid 1-cyclopentyl-ethyl ester represented by Formula XII,which exhibits unexpected fruity, green and fresh accord with wine-likewoody, spicy and sweet notes, very toppy and multifaceted, and a methodof improving, enhancing or modifying a fragrance formulation through theaddition of an olfactory acceptable amount of this ethyl ester.

Another embodiment of the present invention relates to novel compoundsrepresented by Formula XIII, 1,2,4-trimethyl-cyclohex-3-enecarboxylicacid ethyl ester, and Formula XIV,1,3,5-trimethyl-cyclohex-3-enecarboxylic acid ethyl ester, which exhibitunexpected complex fragrance effect of fruity, cassis (blackcurrant)-like, added freshness of citrus (grape fruit), slightly earthyand herbaceous with an olibanum aspect, and a method of improving,enhancing or modifying a fragrance formulation through the addition ofthese ethyl esters.

Another embodiment of the present invention relates to a novel compound13-methyl-3a,4,5,6,7,8,9,10,11,13a-decahydro-1H,3H-2-oxa-cyclopentacyclododecenerepresented by Formula XV, which exhibits an interesting combination offruity, woody, musky, clean, green, fresh, sweet and animalic notes,very desirable, caring, sensual, very powdery and soft with a uniquetobacco-like quality. Its ambery and musky notes provide additionalbody, and a method of improving, enhancing or modifying a fragranceformulation through the addition of an olfactory acceptable amount ofthis compound.

Another embodiment of the present invention relates to a fragrancecomposition comprising the novel compounds provided above.

Another embodiment of the present invention relates to a fragranceproduct comprising the compounds provided above.

Another embodiment of the present invention relates to a method ofimproving, enhancing or modifying a fragrance formulation through theaddition of an olfactory acceptable amount of the novel compoundsprovided above.

These and other embodiments of the present invention will be apparent byreading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

It is intended herein that the compounds described herein includeisomeric mixtures of such compounds, as well as those isomers that maybe separated using techniques known to those having skill in the art.Suitable techniques include chromatography such as high performanceliquid chromatography, referred to as HPLC, and particularly silica gelchromatography and gas chromatography trapping known as GC trapping.Yet, commercial products are mostly offered as isomeric mixtures.

The preparation of the compounds of the present invention is detailed inthe Examples. Materials were purchased from Aldrich Chemical Companyunless noted otherwise.

The use of the compounds of the present invention is widely applicablein current perfumery products, including the preparation of perfumes andcolognes, the perfuming of personal care products such as soaps, showergels, and hair care products, fabric care products, air fresheners, andcosmetic preparations. The present invention can also be used to perfumecleaning agents, such as, but not limited to detergents, dishwashingmaterials, scrubbing compositions, window cleaners and the like.

In these preparations, the compounds of the present invention can beused alone or in combination with other perfuming compositions,solvents, adjuvants and the like. The nature and variety of the otheringredients that can also be employed are known to those with skill inthe art. Many types of fragrances can be employed in the presentinvention, the only limitation being the compatibility with the othercomponents being employed. Suitable fragrances include but are notlimited to fruits such as almond, apple, cherry, grape, pear, pineapple,orange, strawberry, raspberry; musk, flower scents such aslavender-like, rose-like, iris-like, carnation-like. Other pleasantscents include herbal and woodland scents derived from pine, spruce andother forest smells. Fragrances may also be derived from various oils,such as essential oils, or from plant materials such as peppermint,spearmint and the like.

A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891,the contents of which are incorporated by reference as if set forth inits entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

The compounds of the present invention can be used in combination with acomplementary fragrance compound. The term “complementary fragrancecompound” as used herein is defined as a fragrance compound selectedfrom the group consisting of 2-[(4-methylphenyl)methylene]-heptanal(Acalea), iso-amyl oxyacetic acid allylester (Allyl Amyl Glycolate),(3,3-dimethylcyclohexyl)ethyl ethyl propane-1,3-dioate (Applelide),(E/Z)-1-ethoxy-1-decene (Arctical),2-ethyl-4-(2,2,3-trimethyl-3-cyclo-penten-1-yl)-2-buten-1-ol (Bacdanol),2-methyl-3-[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)oxy]exo-1-propanol(Bornafix), 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one(Cashmeran), trimethylcyclopentenylmethyloxabicyclooctane (Cassiffix),1,1-dimethoxy-3,7-dimethyl-2,6-octadiene (Citral DMA),3,7-dimethyl-6-octen-1-ol (Citronellol),3A,4,5,6,7,7A-hexahydro-4,7-methano-1H-inden-5/6-yl acetate (Cyclacet),3A,4,5,6,7,7A-hexahydro-4,7-methano-1H-inden-5/6-yl propinoate(Cyclaprop), 3A,4,5,6,7,7A-hexahydro-4,7-methano-1G-inden-5/6-ylbutyrate (Cyclobutanate),1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-2-buten-1-one (Delta Damascone),3-(4-ethylphenyl)-2,2-dimethyl propanenitrile (Fleuranil),3-(O/P-ethylphenyl) 2,2-dimethyl propionaldehyde (Floralozone),tetrahydro-4-methyl-2-(2-methylpropyl)-2H-pyran-4-ol (Floriffol),1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran(Galaxolide), 1-(5,5-dimethyl-1-cyclohexen-1-yl)pent-4-en-1-one(Galbascone), E/Z-3,7-dimethyl-2,6-octadien-1-yl acetate (GeranylAcetate), a-methyl-1,3-benzodioxole-5-propanal (Helional),1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,6-heptadien-3-one (Hexalon),(Z)-3-hexenyl-2-hydroxybenzoate (Hexenyl Salicylate, CIS-3),4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one (Ionone α),1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1-one(Iso E Super), methyl 3-oxo-2-pentylcyclopentaneacetate (Kharismal),2,2,4-trimethyl-4-phenyl-butanenitrile (Khusinil),3,4,5,6,6-pentamethylhept-3-en-2-one (Koavone),3/4-(4-hydroxy-4-methyl-pentyl) cyclohexene-1-carboxaldehyde (Lyral),3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one (MethylIonone γ), 1-(2,6,6-trimethyl-2-cyclohexen-1-yl) pent-1-en-3-one (MethylIonone α Extra, Methyl Ionone N), 3-methyl-4-phenylbutan-2-ol(Muguesia), cyclopentadec-4-en-1-one (Musk Z4),3,3,4,5,5-pentamethyl-11,13-dioxatricyclo[7.4.0.0<2,6>]tridec-2(6)-ene(Nebulone), 3,7-dimethyl-2,6-octadien-1-yl acetate (Neryl Acetate),3,7-dimethyl-1,3,6-octatriene (Ocimene), ortho-tolylethanol (Peomosa),3-methyl-5-phenylpentanol (Phenoxanol), 1-methyl-4-(4-methyl-3-pentenyl)cyclohex-3-ene-1-carboxaldehyde (Precyclemone B),4-methyl-8-methylene-2-adamantanol (Prismantol),2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (Sanjinol),2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol(Santaliff), Terpineol, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde(Triplal), decahydro-2,6,6,7,8,8-hexamethyl-2H-indeno[4,5-B]furan(Trisamber), 2-tert-butylcyclohexyl acetate (Verdox),4-tert-butylcyclohexyL acetate (Vertenex), acetyl cedrene (Vertofix),3,6/4,6-dimethylcyclohex-3-ene-1-carboxaldehyde (Vertoliff), and(3Z)-1-[(2-methyl-2-propenyl)oxy]-3-hexene (Vivaldie).

The terms “fragrance formulation”, “fragrance composition”, and “perfumecomposition” mean the same and refer to a consumer composition that is amixture of compounds including, for example, alcohols, aldehydes,ketones, esters, ethers, lactones, nitriles, natural oils, syntheticoils, and mercaptans, which are admixed so that the combined odors ofthe individual components produce a pleasant or desired fragrance. Thefragrance formulation of the present invention is a consumer compositioncomprising a compound of the present invention. The fragranceformulation of the present invention comprises a compound of the presentinvention and further a complementary fragrance compound as definedabove.

The term “fragrance product” means a consumer product containing afragrance ingredient that adds fragrance or masks malodor. Fragranceproducts may include, for example, perfumes, colognes, bar soaps, liquidsoaps, shower gels, foam baths, cosmetics, skin care products such ascreams, lotions and shaving products, hair care products for shampooing,rinsing, conditioning, bleaching, coloring, dyeing and styling,deodorants and antiperspirants, feminine care products such as tamponsand feminine napkins, baby care products such as diapers, bibs andwipes, family care products such as bath tissues, facial tissues, paperhandkerchiefs or paper towels, fabric products such as fabric softenersand fresheners, air care products such as air fresheners and fragrancedelivery systems, cosmetic preparations, cleaning agents anddisinfectants such as detergents, dishwashing materials, scrubbingcompositions, glass and metal cleaners such as window cleaners,countertop cleaners, floor and carpet cleaners, toilet cleaners andbleach additives, washing agents such as all-purpose, heavy duty, andhand washing or fine fabric washing agents including laundry detergentsand rinse additives, dental and oral hygiene products such astoothpastes, tooth gels, dental flosses, denture cleansers, dentureadhesives, dentifrices, tooth whitening and mouthwashes, health care andnutritional products and food products such as snack and beverageproducts. The fragrance product of the present invention is a consumerproduct that contains a compound of the present invention. The fragranceproduct of the present invention contains a compound of the presentinvention and further a complementary fragrance compound as definedabove.

The term “improving” in the phrase “improving, enhancing or modifying afragrance formulation” is understood to mean raising the fragranceformulation to a more desirable character. The term “enhancing” isunderstood to mean making the fragrance formulation greater ineffectiveness or providing the fragrance formulation with an improvedcharacter. The term “modifying” is understood to mean providing thefragrance formulation with a change in character.

The term “olfactory acceptable amount” is understood to mean the amountof a compound in a fragrance formulation, wherein the compound willcontribute its individual olfactory characteristics. However, theolfactory effect of the fragrance formulation will be the sum of effectof each of the fragrance ingredients. Thus, the compound of the presentinvention can be used to improve or enhance the aroma characteristics ofthe fragrance formulation, or by modifying the olfactory reactioncontributed by other ingredients in the formulation. The olfactoryacceptable amount may vary depending on many factors including otheringredients, their relative amounts and the olfactory effect that isdesired.

The amount of the compounds of the present invention employed in afragrance formulation varies from about 0.005 to about 70 weightpercent, preferably from 0.005 to about 50 weight percent, morepreferably from about 0.5 to about 25 weight percent, and even morepreferably from about 1 to about 10 weight percent. Those with skill inthe art will be able to employ the desired amount to provide desiredfragrance effect and intensity. In addition to the compounds of thepresent invention, other materials can also be used in conjunction withthe fragrance formulation to encapsulate and/or deliver the fragrance.Some well-known materials are, for example, but not limited to,polymers, oligomers, other non-polymers such as surfactants,emulsifiers, lipids including fats, waxes and phospholipids, organicoils, mineral oils, petrolatum, natural oils, perfume fixatives, fibers,starches, sugars and solid surface materials such as zeolite and silica.

When used in a fragrance formulation these ingredients provideadditional notes to make a fragrance formulation more desirable andnoticeable, and add the perception of value. The odor qualities found inthese materials assist in beautifying and enhancing the finished accordas well as improving the performance of the other materials in thefragrance.

The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art. Such modifications are understoodto be within the scope of this invention. As used herein all percentagesare weight percent unless otherwise noted, ppm is understood to standfor parts per million, L is understood to be liter, mL is understood tobe milliliter, g is understood to be gram, Kg is understood to bekilogram, mol is understood to be mole, psi is understood to bepound-force per square inch, and mmHg be millimeters (mm) of mercury(Hg). IFF as used in the examples is understood to mean InternationalFlavors & Fragrances Inc., New York, N.Y., USA.

Example I

Preparation of1,1-Diethyl-4,6-dimethyl-1,3,3a,4,7,7a-hexahydro-isobenzofuran (FormulaIa), 1,1-Diethyl-4,6-dimethyl-1,3,3a,6,7,7a-hexahydro-isobenzofuran(Formula Ib),1,1-Diethyl-5,7-dimethyl-1,3,3a,4,7,7a-hexahydro-isobenzofuran (FormulaHa) and 1,1-Diethyl-5,7-dimethyl-1,3,3a,4,5,7a-hexahydro-isobenzofuran(Formula IIb)

A mixture of Formula I 1,1-diethyl-4,6-dimethyl-1,3,3a,4 (or6),7,7a-hexahydro-isobenzofuran including Formula Ia and Ib and FormulaII 1,1-diethyl-5,7-dimethyl-1,3,3a,4,5 (or 7),7a-hexahydro-isobenzofuranincluding Formula IIa and IIb was prepared as described in EXAMPLE V ofU.S. application Ser. No. 13/888,713 filed May 7, 2013. Formula I andFormula II had a weight ratio of about 80:20.

The mixture obtained in the above preparation possessed the NMR spectralcharacteristics of: ¹H NMR (500 MHz, CDCl₃): 5.11-5.89 ppm (m, 1H),2.89-4.06 ppm (m, 2H), 2.50 & 2.59 ppm (2s, 1H), 1.80-2.41 ppm (m, 2H),1.62-1.79 ppm (m, 5H), 1.19-1.62 ppm (m, 4H), 0.82-1.17 ppm (m, 9H).

The mixture of Formula I and II was described as having woody and spicynotes with leather-like quality.

Example II

Preparation of 5-Methyl-hept-5-enal (Formula V) and2,4-Dimethyl-hex-4-enal (Formula VI)

Isoprene reacted with ehtylene gas in the presence of an appropriatecobalt catalyst to yield 4-methyl-hexa-1,4-diene, which was thensubjected to hydroformylation reaction to afford the mixture of5-methyl-hept-5-enal and 2,4-dimethyl-hex-4-enal.

Formula V obtained in the above preparation possessed the NMR spectralcharacteristics of: ¹H NMR (400 MHz, CDCl₃): 9.77 (t, J=1.8 Hz, 1H),5.18-5.32 (m, 1H), 2.41 (td, J=7.3, 1.8 Hz, 2H), 2.08 (t, J=7.6 Hz, 2H),1.53-1.78 (m, 8H)

Formula VI obtained in the above preparation possessed the NMR spectralcharacteristics of: ¹H NMR (400 MHz, CDCl₃): 9.66 (d, J=1.9 Hz, 1H),5.03-5.13 (m, 1H), 1.53-2.56 (m, 9H), 1.06 (d, J=6.9 Hz, 3H)

The mixture of Formula V and VI was described as having a melon-likeozonic note with a green aspect.

Example III

Preparation of 2,4,8-Trimethyl-deca-4,9-dienal (Formula VII)

4,8-Dimethyl-deca-4,9-dienal (commercially available at IFF) was used asthe starting material to provide4,8-dimethyl-2-methylene-deca-4,9-dienal, which was then hydrogenated toafford 2,4,8-trimethyl-deca-4,9-dienal.

¹H NMR (400 MHz, CDCl₃): 9.62 (d, J=2.0 Hz, 1H), 5.68 (ddd, J=17.4,10.1, 7.7 Hz, 1H), 5.11-5.23 (m, 1H), 4.89-4.98 (m, 2H), 2.34-2.55 (m,2H), 2.05-2.17 (m, 1H), 1.92-2.05 (m, 3H), 1.59 (s, 3H), 1.20-1.43 (m,2H), 1.03 (d, J=6.8 Hz, 3H), 0.99 (d, J=6.8 Hz, 3H)

Formula VII was described as having green, floral and muguet notes.

Example IV

Preparation of 5-Ethyl-3-methylhexahydro-1-benzofuran-2(3H)-one (FormulaVIII) and 6-Ethyl-3-methylhexahydro-1-benzofuran-2(3H)-one (Formula IX)

4-Vinylcyclohexene oxide reacted with dimethyl methyl malonate in thepresence of a base to afford the unsaturated lactone in the above, whichwas then subjected to hydrogenation to afford the isomeric mixture of5-ethyl-3-methylhexahydro-1-benzofuran-2(3H)-one and6-ethyl-3-methylhexahydro-1-benzofuran-2(3H)-one.

The mixture obtained in the above preparation possessed the NMR spectralcharacteristics of: ¹H NMR (500 MHz, CDCl₃): 3.68-4.06 (m, 1H),2.14-2.32 (m, 2H), 1.24-2.07 (m, 9H), 1.14-1.27 (m, 3H), 0.89-0.97 (m,3H)

The mixture of Formula VIII and Formula IX was described as havingcreamy and coconut-like notes with woody and slightly animaliccharacters.

Example V

Preparation of Methyl-2-(propan-2-yl)cyclohexyl carbonate (Formula X)

2-Isopropyl phenol was hydrogenated to obtain 2-isopropyl cyclohexanol,which then reacted with an excess amount of dimethylcarbonate in thepresence of catalyst sodium methoxide to affordmethyl-2-(propan-2-yl)cyclohexyl carbonate.

¹H NMR (500 MHz, CDCl₃): 4.47-4.55 (m, 1H), 3.77 (s, 3H), 2.02-2.11 (m,1H), 1.95 (m, 1H), 1.64-1.80 (m, 2H), 0.99-1.53 (m, 6H), 0.80-0.94 (m,6H)

Formula X was described as having fruity, herbaceous, spicy, fresh andwoody notes.

Example VI

Preparation of2-(3-Methoxy-2-propen-1-yl)-6,6-dimethyl-bicyclo[3.1.1]hept-2-ene(Formula XI)

Pinoacetaldehyde (commercially available at IFF) reacted withtrimethylorthoformate (TMOF), methanol (MeOH) and hydrochloric acid(HCl) to obtain2-(3,3-dimethoxypropyl)-6,6-dimethyl-bicyclo[3.1.1]hept-2-ene, whichthen, in the presence of pyridine (Pyr.) and phosphoric acid (H₃PO₄), toprovide2-(3-methoxy-2-propen-1-yl)-6,6-dimethyl-bicyclo[3.1.1]hept-2-ene.

¹H NMR (400 MHz, CDCl₃): 5.92 (dt, J=6.2, 1.6 Hz, 1H), 5.18-5.23 (m,1H), 4.31 (td, J=7.3, 6.2 Hz, 1H), 3.58 (s, 3H), 2.69-2.76 (m, 2H),1.97-2.39 (m, 4H), 1.26 (s, 3H), 1.12-1.17 (m, 1H), 0.82 (s, 3H)

Formula XI was described as having floral, muguet, fresh, green andmelon-like notes with creamy and herbaceous quality.

Example VII

Preparation of But-2-enoic acid 1-cyclopentyl-ethyl ester (Formula XII)

Cyclopentene reacted with carbon monoxide (CO) and hydrogen (H₂) in thepresence of a Wilkinson's catalyst to providecyclopentanecarboxaldehyde, which then reacted with methylmagnesiumchloride (MeMgCl) to provide 1-cyclopentylethanol, which further reactedwith crotonic acid in the presence of p-toluenesulfonic acid (pTSA) toafford product but-2-enoic acid 1-cyclopentyl-ethyl ester.

¹H NMR (500 MHz, CDCl₃): 6.89-6.99 (m, 1H), 5.83 (dq, J=15.6, 1.6 Hz,1H), 4.79-4.88 (m, 1H), 1.92-2.09 (m, 1H), 1.87 (dd, J=6.9, 1.5 Hz, 3H),1.67-1.76 (m, 2H), 1.49-1.65 (m, 4H), 1.18-1.33 (m, 2H), 1.22 (d, J=6.2Hz, 3H)

Formula XII was described as having fruity, green, fresh, woody, spicyand sweet notes.

Example VIII

Preparation of 1,2,4-Trimethyl-cyclohex-3-enecarboxylic acid ethyl ester(Formula XIII) and 1,3,5-Trimethyl-cyclohex-3-enecarboxylic acid ethylester (Formula XIV)

2-Methyl-penta-1,3-diene (954 g) and 2-methyl-acrylic acidethyl ester(1.11 Kg) were charged into an autoclave and heated to 160° C. After 3hours, the reaction temperature was increased to 220° C. (180 psi). Theprogress of the reaction was monitored with gas chromatography (GC)analysis. The reaction mixture was aged for about 8 hours and thendistilled to afford a mixture of1,2,4-trimethyl-cyclohex-3-enecarboxylic acid ethyl ester and1,3,5-trimethyl-cyclohex-3-enecarboxylic acid ethyl ester (1.58 Kg).Formula XIII and Formula XIV had a weight ratio of about 95:5.

The mixture obtained in the above preparation possessed the NMR spectralcharacteristics of: ¹H NMR (400 MHz, CDCl₃): 5.10-5.29 (m, 1H),4.09-4.17 (m, 2H), 2.11-2.75 (m, 1H), 1.86-1.97 (m, 2H), 1.55-1.68 (m,2H), 1.64 (s, 3H), 1.26 (t, J=7.1 Hz, 3H), 1.19 (s, 3H), 0.88 (d, J=6.9Hz, 3H)

The mixture of Formula XIII and Formula XIV was described as havingfruity, fresh, earthy and herbaceous notes.

Example IX

Preparation of13-Methyl-3a,4,5,6,7,8,9,10,11,13a-decahydro-1H,3H-2-oxa-cyclopentacyclododecene(Formula XV)

13-Methyl-3a,4,5,6,7,8,9,10,11,13a-decahydro-1H,3H-2-oxa-cyclopentacyclododecenewas prepared following below steps:

Step 1: Muscogene (478 g, 2.4 mol), sodium acetate (63 g, 0.76 mol) andethyl acetate (500 mL) were charged into a flask. The reaction wascooled to 0° C. While the temperature was maintained at 0° C., peraceticacid (32%, 500 mL, 2.38 mol) was dropped in over an hour and thereaction mixture was stirred for another 2 hours. Saturated sodiumcarbonate solution (100 mL) and toluene (50 mL) were added. The organiclayer was separated and washed with brine (200 mL). The crude waspurified to provide 3,15-dioxa-tricyclo[11.3.0.0*2,4*]hexadecane (462 g,˜85% yield).

Step 2: 3,15-Dioxa-tricyclo[11.3.0.0*2,4*]hexadecane from Step 1 (260 g,1.16 mol) was mixed with lithium iodide (2.5 g, 18.7 mmol) and heated to200° C. for 8 hours. The reaction was then cooled down and washed withwater (500 mL). The crude was distilled to providedodecahydro-2-oxa-cyclopentacyclododecen-4-one (138 g, ˜53% yield).

Step 3: Methyl magnesium chloride solution (3 M in THF, 190 mL, 0.56mol) and toluene (100 mL) were mixed and heated to reflux. A solution ofdodecahydro-2-oxa-cyclopentacyclododecen-4-one from Step 2 (0.56 mol) intoluene (100 mL) was then added in dropwise. The reaction mixture wasstirred for another 2 hours and then cooled down. Acetic acid (200 g)and water (200 g) were added. The organic layer was separated and washedwith brine (200 mL) to provide a crude containing4-methyl-dodecahydro-2-oxa-cyclopentacyclododecen-4-ol.

Step 4: Crude 4-methyl-dodecahydro-2-oxa-cyclopentacyclododecen-4-ol(133 g) from Step 3 was dissolved in toluene (1 L). p-Toluenesulfonicacid (pTSA) (4 g) was added and the reaction was heated to reflux with awater trap. After 8 hours, there was no more water separated. Thereaction was cooled and washed with sodium carbonate solution. Furtherdistillation afforded13-methyl-3a,4,5,6,7,8,9,10,11,13a-decahydro-1H,3H-2-oxa-cyclopentacyclododecene(101 g, ˜82% yield).

¹H NMR (500 MHz, CDCl₃): 5.29 (m, 1H), 3.18-3.99 (m, 4H), 0.95-2.65 (m,18H), 1.63 (s, 3H)

Formula XV was described as having fruity, woody, musky, clean, green,fresh, sweet and animalic notes with a unique tobacco-like quality.

What is claimed is:
 1. The compound but-2-enoic acid 1-cyclopentyl-ethylester.
 2. A fragrance product containing an olfactory acceptable amountof the compound of claim
 1. 3. The fragrance product of claim 2, whereinthe fragrance product is selected from the group consisting of aperfume, a cologne, toilet water, a cosmetic product, a personal careproduct, a fabric care product, a cleaning product and an air freshener,a bar soap, a liquid soap, a shower gel, a foam bath, a cosmetic, a skincare product, a hair care product, a deodorant, an antiperspirant, afeminine care product, a baby care product, a family care product, afabric product, an air care product, a fragrance delivery system, acosmetic preparation, a cleaning agent, a disinfectant, a washing agent,a dental and oral hygiene product, a health care and nutritional productand a food product.
 4. The fragrance product of claim 3, wherein thecleaning product is selected from the group consisting of a detergent, adishwashing material, a scrubbing composition, a glass cleaner, a metalcleaner, a countertop cleaner, a floor cleaner, a carpet cleaner, atoilet cleaner and a bleach additive.
 5. The fragrance product of claim3, wherein the washing agent is selected from the group consisting of alaundry detergent and a rinse additive.
 6. A fragrance formulationcontaining an olfactory acceptable amount of but-2-enoic acid1-cyclopentyl-ethyl ester.
 7. The fragrance formulation of claim 6,wherein the olfactory acceptable amount is from about 0.005 to about 50weight percent of the fragrance formulation.
 8. The fragranceformulation of claim 6, wherein the olfactory acceptable amount is fromabout 0.5 to about 25 weight percent of the fragrance formulation. 9.The fragrance formulation of claim 6, wherein the olfactory acceptableamount is from about 1 to about 10 weight percent of the fragranceformulation.
 10. The fragrance formulation of claim 6 further comprisinga product selected from the group consisting of a perfume, a cologne,toilet water, a cosmetic product, a personal care product, a fabric careproduct, a cleaning product, and an air freshener.
 11. The fragranceformulation of claim 10, wherein the cleaning product is selected fromthe group consisting of a detergent, a dishwashing composition, ascrubbing compound, and a window cleaner.
 12. The fragrance formulationof claim 6 further comprising a material selected from the groupconsisting of a polymer, an oligomer and a non-polymer.
 13. Thefragrance formulation of claim 12, wherein the non-polymer is selectedfrom the group consisting of a surfactant, an emulsifier, a fat, a wax,a phospholipid, an organic oil, a mineral oil, a petrolatum, a naturaloil, a perfume fixative, a fiber, a starch, a sugar and a solid surfacematerial.
 14. The fragrance formulation of claim 13, wherein the solidsurface material is selected from the group consisting of zeolite andsilica.
 15. A method of improving, enhancing or modifying a fragranceformulation through the addition of an olfactory acceptable amount ofbut-2-enoic acid 1-cyclopentyl-ethyl ester.
 16. The method of claim 15,wherein the olfactory acceptable amount is from about 0.005 to about 50weight percent of the fragrance formulation.
 17. The method of claim 15,wherein the olfactory acceptable amount is from about 0.5 to about 25weight percent of the fragrance formulation.
 18. The method of claim 15,wherein the olfactory acceptable amount is from about 1 to about 10weight percent of the fragrance formulation.